Simultaneous determination by ultra-performance liquid chromatography–atmospheric pressure chemical ionization time-of-flight mass spectrometry of nitrated and oxygenated PAHs found in air and soot particles

Abstract

An ultra-performance liquid chromatographic-atmospheric pressure chemical ionization time-of-flight mass spectrometric (UPLC-APCIToFMS) method for rapid analysis of twelve nitrated polycyclic aromatic hydrocarbons (NPAHs) and nine oxygenated polycyclic aromatic hydrocarbons (OPAHs) in particle samples has been developed. The extraction step using pressurized liquid extraction was optimized by experimental design methods and the concentrated extracts were analyzed without further clean-up. Matrix effects resulting in suppression or enhancement of the response during the ionization step were not observed. The suitability of the developed method is demonstrated by analysis of six different particle samples including standard reference materials, atmospheric particles collected by a high-volume sampler at an urban background site, and a soot sample from a burner. Results from these measurements showed clear differences between the different kinds of samples. Concentrations from reference materials are in good agreement with those from previous studies. Additionally a clear seasonal trend could be observed in atmospheric NPAH and OPAH concentrations found in real samples, with higher concentrations in winter.

UHPLC-(+)APCI-MS/MS determination of oxygenated and nitrated polycyclic aromatic hydrocarbons in airborne particulate matter and tree barks collected in Buenos Aires city

“…Screening experiments showed that to obtain an efficient NPAHs and OPAHs Under the optimal mentioned conditions, the analytes were eluted within 3.0 minutes from the column within a 5.0 minutes total run cycle, which was considerably shorter than the ones reported by Lintelmann et al [32] and Mirivel et al [33].…”

Recent analytical methods for atmospheric polycyclic aromatic hydrocarbons and their derivatives

“…To monitor atmospheric concentrations of PAHQs, methods using LC–MS or LC‐MS/MS were typically accompanied with the ionization of PAHQs using APCI (Delhomme, Millet, & Herckes, ; Jakober, Charles, Kleeman, & Green, ; Lintelmann, Fischer, & Matuschek, ; Mirivel, Riffault, & Galloo, ; O'Connell, Haigh, Wilson, & Anderson, ; Walgraeve et al, ). In HPLC methods, PAHQs were converted to fluorescent derivatives and detected using FL (Kishikawa, Wada, Ohba, Nakashima, & Kuroda, ).…”

Factors and Trends Affecting the Identification of a Reliable Biomarker for Diesel Exhaust Exposure

“…In this regard, the recently published work of Mirivel et al is perhaps the most significant and worthy of the closest scrutiny (Mirivel et al, 2010). As shown in Table 4, when the levels of individual oxygenated-PAHs from diesel soot are compared with other potential sources, including kerosene soot as well as reference PM for urban air, indoor air, and vehicle exhaust, an interesting pattern emerges.…”

“…Monocyclic and polycyclic quinones, such as those present in diesel exhaust, are generally highly reactive and capable of forming albumin and hemoglobin adducts that are stable for periods of a month to four months, respectively (Granath et al, 1992). Although some polycyclic quinones are too reactive to be absorbed intact through the lungs without first being scavenged by other nucleophilic receptors, diesel exhaust contains several unique quinones, such as 9,10-phenanthroquinone and 2-methyl-9,10-anthraquinone, whose reactivity may be sufficiently low that blood protein adducts may be detected following an exposure (Mirivel et al, 2010). An example of a recent success in this regard is the use of 1,2-naphthoquinone albumin adduct as a biomarker for occupational naphthalene exposure in coke-oven workers (Waidyanatha et al, 2004).…”